ICMCTF2007 Session B5-3: Properties and Characterization of Hard Coatings and Surfaces

Tuesday, April 24, 2007 8:00 AM in Room Golden West

Tuesday Morning

Time Period TuM Sessions | Abstract Timeline | Topic B Sessions | Time Periods | Topics | ICMCTF2007 Schedule

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8:00 AM B5-3-1 Stress, Interfacial Effects and Mechanical Properties of Nanoscale Multilayered Coatings
G. Abadias (Universite de Poitiers, France); S.M. Dub (NAS of Ukraine); C. Tromas, C. Jaouen, A. Michel (Universite de Poitiers, France)

Mechanical behaviour and stability of thin films consisting of alternating nanolayers has been the subject of a great research activity over the past decade due to the technological impact of such nanoscale systems for protective hard coatings1. Original elastic and mechanical properties have been reported in a large variety of multilayers due to the high interface density and small-scale dimensions associated with these systems. For example, a softening of shear elastic constants or enhancement of hardness and tensile strength as compared to the rule of mixture values have been reported in metal/metal, nitride/nitride or metal/nitride systems. The present communication will focus on the elastic and plastic properties of three nanolayered systems, namely TiN/Cu, ZrN/W and Mo/Ni, corresponding to different crystal structure and lattice mismatch combinations. They were grown epitaxially on either MgO(001) or Al2O3(1120) substrates by a dual ion beam sputtering techniques. Low-angle and high-angle X-ray diffraction experiments as well as Transmission Electron Microscopy observations were used to characterize the microstructure and crystalline orientation, structure of interfaces and type of growth defects. Mechanical properties were studied by nanoindentation tests using a Berkovich tip and coupled with Atomic Force Microscopy surface observations around the indents. Also, a combined FIB-TEM technique was implemented to image the deformed nanolaminates beneath the indentor. The following issues will be addressed: Stress and intermixing in Mo/Ni multilayers: influence on elastic properties2 and mechanical behaviour in TiN/Cu3 and ZrN/W multilayers.

1S.A. Barnett and A. Madan, Scripta Materialia 50, 739 (2004)

2F. Martin, C. Jaouen, J. Pacaud, G. Abadias et al., Phys. Rev. B. 71, 045422 (2005)

3G. Abadias, Y. Y. Tse, A.Michel, C. Jaouen, M. Jaouen, Thin Solid Films 433, 166 (2003).

8:40 AM B5-3-3 Stress Gradients in TiN Coatings
R. Machunze, G.C.A.M Janssen (Delft University of Technology, Netherlands)

Titanium nitride films (TiN) are used amongst other applications as wear-protecting coatings and as diffusion barrier layers. Control of stress in these films enables improvement in the performance of these coatings.

TiN thin films have been deposited on 100mm Si wafers by reactive magnetron sputtering from a Ti target in an industrial coating system. During deposition (dep. rate approx. 0.1nm/s) at 5kW power, 125V bias voltage, 450°C dep. temperature and 4x10-3mbar pressure, the samples performed a planetary motion in front of the target (target size 600x120mm2). A thin Ti layer was deposited before for better adhesion of the TiN film.

From wafer curvature before and after deposition the stress was inferred. At all thicknesses the stress was compressive, however these films show a more compressive stress with increasing film thickness. We measured 1.4GPa compressive stress for a 30nm thick film and 1.6GPa compressive stress for a 380nm thick film, both grown under identical conditions. The same tendency of thickness dependent stress has been reported by us for Cr films and associated with evolutionairy grain growth [APL 85 3086 (2004)]. Our results are in contrast to the stress thickness relation on work steel substrates reported by Kamminga [JAP 88 6332 (2000)], who found less compressive stress in thicker TiN films. We will discuss the thickness dependent stress in terms of the microstructure of the TiN film to elucidate this different stress behaviour.

9:00 AM B5-3-6 The Effect of Cu Content on the Microstructures, Mechanical and Antibacterial Properties of CrCuN Nanocomposite Coatings Deposited by Pulsed DC Reactive Magnetron Sputtering
Y.C. Kuo, C.J. Wang (National Taiwan University of Science and Technology, Taiwan); J.-W. Lee, Y.J. Chang (Tung Nan Institute of Technology, Taiwan)
The nanocomposite CrCuN thin films with Cu content ranging from 1.6 to 24.2 at.% have been deposited at a substrate temperature at 300°C by a bipolar asymmetric pulsed DC reactive magnetron sputtering system. Different Cu contents of thin films were achieved by changing the power ratios of Cr/Cu targets. An optical emission spectrometer was employed to monitor the stability of plasma during the sputtering process. The microstructures of thin films were examined by scanning electron microscopy(SEM) and transmission electron microscopy(TEM). The nanoindentation and nanoscratch tests were adopted to evaluate the nanomechanical properties of CrCuN coatings. The antimicrobial effect against Escherichia coli was explored. For thin films with higher than 15 at% Cu, the coefficient of friction decreases with increasing Cu content. A high hardness, low scratch coefficient and good antibacterial properties are found in the coatings with 15.6 at.% Cu in this work.
9:20 AM B5-3-7 Thermal Stability and Oxidation Behaviour of CrAlN Coatings
I. Azkona (METAL ESTALKI, S. L., Spain); J.A. Garcia, M.J. Diaz, R. Martinez, R.J. Rodriguez (Asociacion de la Industria Navarra (AIN), Spain)

This article gathers the results of a comparative study of the oxidation behaviour and the tribomechanical properties of a series of different CrAlN coatings subjected to thermal annealing cycles in an atmosferic furnace.

CrAlN coatings with different Cr-Al stoichiometry were deposited by using of a cathodic arc PVD machine. The behaviour of these coatings has been compared with the oxidation performance of nc-CrAlN/Si3N4 nanocomposite coating and with the more conventional TiAlN coating deposited in rotary arc PVD equipment.

Ultramicrohardness, friction and wear resistance measures were carried out before and after thermal annealing in order to study the evolution of the tribomechanical properties. The oxidation process, at different temperatures was studied by means of GDOES analysis looking for the evolution of the composition in depth for the oxygen and other elements. These profiles and the microstructure of the coatings were also investigated by FE-SEM.

As a conclusion this paper looks for the relations between the microstructure, compostion and tribological properties of the different coatings before and after the oxidation experiments.

9:40 AM B5-3-8 Erosion Resistance of BC and CrN Coatings
R.A. Sailer, K. Mattson, D.L. Schulz (North Dakota State University)
This paper compares experimental results for the erosion and hardness testing of CrN and BC coatings on ductile (M-2 steel and Al-2024) substrates using a custom-built gas jet erosion test rig. Aluminum oxide particles ranging in size from 10 to 50 µm were used as the erodent with the velocity and angle of impact being varied from 50 to 130 m/s and from 15 to 90 degrees, respectively, under the initial guidelines of ASTM G-76 "Standard Test Method for Conducting Erosion Tests by Solid Particle Impingement Using Gas Jets". Previous work has demonstrated that this standard may be well suited for measuring the erosive wear of bulk materials and thicker coatings; however, the accuracy of the method is limited when assaying coatings less than 2 µm in thickness. Previous characterization of the erosive wear of CrN coatings on M-2 steel provided the basis for a new mathematical model for erosive wear of brittle coatings on ductile substrates. The validity of this model will be examined with data from BC films over both M-2 steel and Al-2024.
10:00 AM B5-3-9 Synthesis and Characterisation of Cr-B-N Coatings Deposited by Cathodic Arc Plasma Deposition
K. Polychronopoulou (University of Cyprus); J. Neidhardt (University of Leoben, Austria); M. Kokonou, C. Rebholz (University of Cyprus); B. Sartory, R. Kaindl, R. Tessadri (University of Innsbruck, Austria); M.A. Baker (University of Surrey, United Kingdom); M. O'Sullivan (Plansee SE, Austria); A. Reiter (OC Oerlikon Balzers Coating AG, Liechtenstein); C. Mitterer (Montanuniversität Leoben, Austria)
Recent advantages in the area of manufacturing applications stimulate the development of new functional coating materials that provide excellent combination of mechanical, chemical and tribological properties. In this study we report the synthesis and characterization of nanocomposite Cr-B-N coatings (containing ~ 8 at.% of boron with different Cr/N ratios) deposited onto various substrates by high-rate reactive cathodic arc evaporation of Cr/B (80/20 at.%) targets at 500°C using a commercial Balzers RCS system. The composition, structure, mechanical and tribological properties of the as deposited and vacuum annealed coatings were determined using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and transmission electron spectroscopy (TEM), in combination with nanoindentation and ball-on-disc sliding experiments. XRD patterns exhibited reflections corresponding to randomly orientated CrN crystallites for Cr-B-N coatings with Cr/N ratios between ~1 and ~3. No crystalline BN or Cr2N phases were observed, whereas after vacuum annealing at 700°C peaks attributable to the Cr2N phase emerged during stress-temperature measurements. The hardness and elastic modulus values increased from 18-23 GPa and 210-240 GPa, respectively, with decreasing Cr/N ratios. Ball-on-disc tests at room temperature revealed decreasing friction coefficient values from 0.8 to 0.4 for these coatings (with decreasing Cr/N ratios), whereas values between 0.5-0.6 were obtained at 500°C. Raman studies revealed mainly chromium oxide after tribological experiments, a phase considered of playing major role in the wear mechanism.
10:20 AM B5-3-10 Synthesis and Characterization of Zr(N,O) Thin Films on AISI 304 Stainless Steel by Ion Plating
J.-H. Huang, Z.-E Tsai, G.-P. Yu (National Tsing Hua University, Taiwan)
Transition metal oxynitrides have become emerging decorative coating materials due to their adjustable coloration and high hardness and corrosion resistance. This research studied the effect of oxygen content on the coloration, mechanical properties and corrosion resistance of Zr(N,O) thin films deposited on AISI 304 stainless steel using hollow cathode discharge ion plating. The Zr/N/O ratios of the Zr(N,O) films determined using XPS, which indicated three kinds of bondings: ZrN, Zr(NO) and ZrO2. The color of the Zr(N,O) thin film changed from golden yellow to blue and then slate blue with increasing oxygen content. XRD patterns revealed that phase separation of ZrN and m-ZrO2 occurred at the oxygen content between 31.2 and 49.6 %. ZrN single phase existed at O < 18.1 %, while m-ZrO2 phase was prevailed at O > 40.3 at%. Phase separation lowered the hardness of the Zr(N,O) films as ZrO2 fraction < 40 %. When ZrO2 became major phase (> 50 %), the hardness of the films followed Vigard's law, possibly due to the change of distribution of the ZrO2 phase. The residual stress in ZrN phase was higher than that in ZrO2, and the residual stress decreased for the specimen containing 30 to 40 % of ZrO2. For the samples containing more than 44% of ZrO2, the average residual stress was close to that in ZrO2 phase. The corrosion resistance was evaluated by salt spray test and potentiodynamic scan in two solutions: H2SO4 + KSCN and 5% NaCl solutions. From the results of potentiodynamic scan, corrosion resistance increased as the packing density increased and the film thickness was not a crucial factor on Icorr; moreover, the electrical conductivity of the film was another significant factor on corrosion resistance. The results also showed consistent trend in the two solutions.
10:40 AM B5-3-11 Fatigue and Corrosion-Fatigue Performance of a SAE Q&T 4340 Steel Coated with a Ti/TiAlN/WC/C Film, Deposited by Arc Enhanced Magnetron Sputtering
C.J. Villalobos-Gutiérrez (Ciudad Universitaria, Venezuela); A. Piñeiro-Jiménez, J.G. La Barbera-Sosa, M.H. Staia, E.S. Puchi-Cabrera (Universidad Central de Venezuela)
The fatigue and corrosion-fatigue behavior of a SAE Q&T 4340 steel both uncoated and coated commercially with a TiAlN/WC/C bilayer (Balinit® Hardlube) film has been investigated. For this purpose, a number of tensile and fatigue samples were machined according to the specified standards. Fatigue tests were carried out both in air and in a 3 wt% NaCl solution. The TiAlN/WC/C coating had a thickness of approximately 2 µm and it is constituted of two different layers, one of TiAlN and other of WC/C. The first layer has twice the thickness of the second. The comparison of the static mechanical properties of the uncoated and coated samples indicated an increase of approximately 40 MPa in the yield stress and of 60 MPa in the ultimate tensile stress of the coated material. Fatigue tests were conducted under rotating bending conditions at four different maximum alternating stresses, less than the yield stress of the corresponding condition. Such experiments allowed the determination of the Wöhler curves of the uncoated and coated samples and the experimental S-N data were modeled employing different approaches published in the literature. The comparison of the Wöhler plots of the uncoated and coated substrate indicated that fatigue life of the coated specimens increased between 5-30% when these were tested in air at maximum alternating stresses in the range of 726-612 MPa. Also, when the uncoated and coated materials were tested in the NaCl solution, an increase in the fatigue life of the coated specimens of approximately 19-55% was observed, at maximum alternating stresses in the same range mentioned above. Regarding the fatigue limit, which was evaluated employing the staircase method, it was determined that the presence of the coating gave rise to an increase of approximately 12% in such a parameter.
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